咪唑-金属配合物的合成、性质及其与DNA的作用机理

Three hexakis（imidazole）metallo complexes of Co, Cd and Ni were synthesized and spectroscopically characterized. The crystal and molecular structures have been determined by X-ray crystallography analysis. The metal ions have an octahedral geometry with the MN6 chromophore. The electrochemical experimental results indicate that both [Co（Im）6]C12·2HCl·2H2O （1） and [Ni（Im）6]C12·4H2O （3） [Im=imidazole] could interact with DNA mainly by intercalation.     

微波辐射下LaNaY沸石的水热交换反应

报道微波辐射应用于ＮａＹ沸石与Ｌａ（ＮＯ＿３）＿３溶液的离子交换反应，结果表明微波辐射可提高Ｌａ￣＋的交换度，缩短交换时间。     

烯烃羰化—步制醇铑系催化新体系的研究

羰基铑催化剂由于其加氢性能较弱，在羰基化反应的研究中，通常仅作为烯烃氢甲酰化制醛的催化剂。产物中得不到醇。本文则报道了以Ｒｈ＿２（ＡｃＯ）＿４和Ｒｈ＿６（ＣＯ）＿１６为催化剂，在一个反应器内进行烯烃氢甲酰化，加氢制醇的研究。系统考察了Ｒｈ／Ｐｂｕ＿３／ＥｔＯＨ催化体系受各种反应条件的影响。在最佳反应条件下，烯烃转化率达１００％。对醇选择性亦在９９．５％以上，正异构比在２以上．为烯烃一步制醇建立了铑系催化新体系。文中并利用红外光谱测定了反应过程的催化剂物种．实验证明，由烯烃一步制醇是由烯烃首先进行氢甲酰化反应，然后由生成的醛进一步加氢成醇的一个串联反应过程。前一步骤反应速度较快，２ｈ内可使９５％以上的烯烃转化为醛，后面由醛加氢成醇则进行缓慢，在１００—１２０℃下，至少２２ｈ，才能使醛全部转化为醇。     

Microwave irradiation assisted synthesis, alkylation reaction, and configuration analysis of aryl pyrogallol[4]arenes

A series of aryl pyrogallol[4]arenes were efficiently synthesized in excellent yields by cyclocondensation of pyrogallol with aromatic aldehydes under microwave irradiation. The structures of aryl pyrogallol[4]arenes were confirmed by characterization of their acylated derivatives. Under microwave irradiation, alkylation reactions of aryl pyrogallol[4]arenes with some alkylating reagents such as n-butyl iodide, benzyl chloride, and ethyl α-chloroacetate were also finished quickly to yield fully O-alkylated products. The ¹H NMR spectra and crystal structures showed that the acylated and alkylated aryl pyrogallol[4]arenes existed mainly in rctt (cis-trans-trans) configuration.     

Structures and energies of coadsorbed CO and H2 on Fe5C2(001), Fe5C2(110), and Fe5C2(100)

Density functional theory calculations have been carried out on the CO/H2 coadsorption on the (001), (110), and (100) surfaces of Fe5C2 for the understanding of the Fischer-Tropsch synthesis (FTS) mechanism. The stable surface species changes with the variation of the H2 and CO coverage. Along with dissociated hydrogen and adsorbed CO in 2-, 3-, and 4-fold configurations, methylidyne (C(s)H) (C(s), surface carbon), ketenylidene (C(s)CO), ketenyl (C(s)HCO), ketene (C(s)H2CO), and carbon suboxide (C(s)C2O2) are computed as thermodynamically stable surface species on Fe5C2(001) and Fe5C2(110) containing both surface iron and carbon atoms. These surface carbon species can be considered as the preliminary stages for FTS. On Fe5C2(100) with only iron atoms on the surface layer, the stable surface species is dissociated hydrogen and CO with top and 2-fold configurations. The bonding nature of these adsorbed carbon species has been analyzed.     

The effect of the third component on butadiene–propylene alternating copolymerization catalyzed by vanadium–aluminum system

The effects of five ethers and four AliBu₂OR's with varied R' on butadiene–propylene alternating copolymerization were investigated. It was found that by adding the proper third component, both the conversion and the catalytic efficiency could be increased. The effect of the third component on the valence state of vanadium ion was also studied. A model of the active center of the ternary-component catalyst system was proposed.     

Hybridized local and charge-transfer excited state fluorophores enabling organic light-emitting diodes with record high efficiencies close to 20%

Pure organic emitters with full utilization of triplet excitons are in high demand for organic light-emitting diodes (OLEDs). Herein, through modulation of electron donors and introduction of phenyl rings as π spacers, we present three pure organic fluorophores (BCz, BTCz and BPTCz) with the hybridized local and charge-transfer (HLCT) excited state feature for OLED fabrication. Importantly, the introduction of π spacers in BPTCz not only enhances locally excited character with a fast radiative decay but also promotes intermolecular interactions to suppress non-radiative decays, contributing to a high solid-state fluorescence efficiency over 90%. Significantly, BPTCz not only endows its doped OLEDs with an external quantum efficiency (EQE) up to 19.5%, but also its non-doped OLED with a high EQE of 17.8%, and these outstanding efficiencies are the state-of-the-art performances of HLCT-based OLEDs.

Three purely organic fluorophores with a hybridized local and charge-transfer excited state feature are presented and enabled organic light-emitting diodes with record high external quantum efficiencies close to 20%.     

Structure and stability of closo-BnHn−2(CO)2 (n = 5–12)

Closo-B_nH_n−2(CO)₂ (n = 5–12), isolobal analogues of closo-C₂B_n−2H_n, have been investigated at the B3LYP/6-311+G^**density functional level of theory. The most stable isomers of closo-B_nH_n−2(CO)₂ are similar to those of closo-C₂B_n−2H_n in geometric patterns apart from closo-B₆H₄(CO)₂, and closo-B_nH_n−2(CO)₂ is much less strained than closo-C₂B_n−2H_n. Energetic analysis identifies closo-B₆H₄(CO)₂, closo-B₁₂H₁₀(CO)₂ and closo-B₁₀H₈(CO)₂ to be most stable, of which the latter two cages have been prepared experimentally. On the basis of the negative and rather large nucleus independent chemical shifts (NICS), closo-B_nH_n−2(CO)₂ are aromatic. To aid further experimental study, the CO stretching frequencies have been computed.     

Preparation and thermal properties of a novel flame-retardant coating

A novel silicone and phosphate modified acrylate (DGTH) was synthesized and characterized by ¹H NMR and FTIR. It was found that DGTH could be cured both by UV radiation and moisture mode with FTIR. The flammability and thermal behavior of the cured film were studied by the limited oxygen index (LOI), thermogravimetric analysis (TG) and real time Fourier transform infrared (RT-FTIR). The LOI value of the cured film is 48 and the TG data shows that the cured film has three characteristic degradation temperature regions, attributing to the decomposition of phosphate and polyurethane to alcohols and isocyanates, thermal pyrolysis of alkyl chains, and decomposition of unstable structures in char, respectively. The RT-FTIR data implies that the degraded products of phosphate form poly(phosphoric acid) further catalyse the breakage of carbonyl groups to form an intumescent char, preventing the samples from further burning.     

Z‐bpy,a New C2‐Symmetric Bipyridine Ligand and Its Application in Enantioselective Copper(I)‐Catalyzed Cyclopropanation of Olefins

A rigid C₂‐symmetric chiral bipyridine ligand Z‐bpy with a triptycene‐like backbone was designed and synthesized from simple chemicals in a scalable route. Using this new ligand, copper(I) catalyzed cyclopropanation of styrenes with commercial ethyl diazoacetate produced various corresponding cyclopropanes in high yields, diastereoselectivity and enantioselectivity up to 97% ee.